Reactive dyestuffs containing hydroxy naphthalene disulphonic acids

ABSTRACT

New reactive dyestuffs which, in the form of the free acid, correspond to the following formula   &lt;IMAGE&gt;   wherein the substituents have the meaning given in the description, are suitable for dyeing and printing materials containing hydroxyl groups or amide groups, in particular cellulose materials.

The present invention relates to new reactive dyestuffs, a process for their preparation and their use.

Reactive dyestuffs which contain an azo compound of naphthalenesulphonic acids as the chromophore are already known from EP-A-299,315, DE-A-1,644,208 and JP-A-61 171,770.

The present invention relates to reactive dyestuffs which, in the form of the free acid, correspond to the following formula ##STR2## wherein R=CH₃ or C₂ H₅,

R¹ =hydrogen or an aliphatic, cycloaliphatic or araliphatic radical,

R² =a radical mentioned under R¹ or a heteroaryl radical or a phenyl radical, wherein the radicals R¹ and R², optionally including a further hetero atom, can form a ring, and

R³ =H or SO₃ H.

Further hetero atoms for ring formation of R² and R¹ are preferably O, NH, NCH₃, NCOCH₃, N--C₂ H₄ SO₂ CH═CH₂, S, SO and SO₂.

Preferred heteroaryl radicals R² and R¹ are 3-aminosulpholane, 2-aminothiazole and 6-amino-2-ethylsulphonylbenzothiazole.

In a preferred embodiment, --NR¹ R² represents the radical of an aliphatic amine, or of a heterocyclic amine in which R¹ and R² together with the common N atom, form a ring.

Examples of substituents are: OH, Cl, F, COOH, SO₃ H, OSO₃ H, SO₂ CH═CH₂, CN, SO₂ CH₂ CH₂ Cl, SO₂ CH₂ CH₂ SO₃ H and NR*--Z, wherein Z represents a heterocyclic reactive group, in particular one of the group comprising the monochloro- and the monofluorotriazine series or of the fluoropyrimidine series.

The cycloaliphatic radicals R¹ are, in particular, 5- or 6-membered cycloalkyl radicals.

The araliphatic radicals R¹ are, in particular, those of the formula ##STR3## wherein n=1-4 and the radical A can be substituted, for example by Cl, NO₂ , COOH, SO₃ H, CH₃, OCH₃ , SO₂ CH₂ CH₂ OSO₃ H or SO₂ CH═CH₂, CH₂ SO₂ CH₂ CH₂ OSO₃ H.

Examples of substituents of the phenyl radicals R² are: OCH₃, OC₂ H₅, OCH₂ CH₂ OH, CH₃, C₂ H₅, --CH(CH₃)₂, F, Cl, Br, COOH, SO₃ H, NO₂ , SO₂ CH₂ CH₂ OSO₃ H, SO₂ CH═CH₂, CH₂ SO₂ CH₂ CH₂ OSO₃ H, CH₂ SO₂ CH═CH₂ and NHZ.

The following examples may be mentioned specifically for R¹ or R² =an aliphatic radical:

CH₃, C₂ H₅, CH₂ CH₂ OH, CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OCH₂ CH₂ OH, CH₂ SO₃ H, CH₂ CH₂ SO₃ H, CH₂ CH₂ OSO₃ H, CH₂ COOH, CH₂ CH₂ COOH, CH₂ CH₂ SO₂ CH₂ CH₂ OSO₃ H , CH₂ CH₂ OCH₂ CH₂ SO₂ CH₂ CH₂ Cl, CH₂ CH₂ OCH₂ CH₂ SO₂ CH═CH₂, CH₂ CH₂ NHCOCH₂ CH₂ COOH, CH₂ CH₂ CH₂ SO₂ CH₂ CH₂ OSO₃ H , CH₂ CH₂ CH₂ SO₂ CH═CH₂, CH₂ CH₂ CH₂ SO₂ CH₂ CH₂ Cl, ##STR4## Examples of cycloaliphatic radicals R¹ and R² are: ##STR5## Araliphatic radicals R¹ are, for example, ##STR6## The following radicals may be mentioned as examples of phenyl radicals R² : ##STR7## Examples of cyclic radicals ##STR8## are ##STR9## Preferred compounds in the context of the formula (1) are those compounds in which R³ represents hydrogen.

Compounds which are furthermore preferred are those in which R¹ and R² independently of one another denote hydrogen or C₁ -C₄ -alkyl, which can be substituted by OCH₃, OC₂ H₅, COOH, OSO₃ H, SO₃ H, OCH₂ CH₂ SO₂ CH₂ CH₂ OSO₃ H, OCH₂ CH₂ SO₂ CH═CH₂, OCH₂ CH₂ SO₂ CH₂ CH₂ Cl, SO₂ CH₂ CH₂ OSO₃ H or SO₂ CH═CH₂ ; in a further preferred embodiment, R¹ denotes hydrogen or C₁ -C₄ -alkyl and R² denotes a phenyl radical, which can be substituted by Cl, OCH₃, CH₃, SO₃ H, NO₂, COOH, CN, SO₂ CH₂ CH₂ OSO₃ H, SO₂ CH═CH₂, CH₂ SO₂ CH₂ CH₂ OSO₃ H or CH₂ SO₂ CH═CH₂ ; in a further preferred embodiment, ##STR10## represents the radical of a cyclic amine, in particular ##STR11##

The invention furthermore relates to a process for the preparation of the dyestuffs of the formula (1), which is characterised in that 2-amino-5-hydroxynaphthalene-1,7-disulphonic acid is first subjected to a condensation reaction with trifluorotriazine in the pH range of 2-6, in particular 3-5, and at temperatures of -5° to +20°, in particular at 0°-5°, if appropriate in the presence of a buffer, to give a difluorotriazine compound, a further fluorine atom is subsequently replaced by an amine radical NR¹ R², and, finally the resulting monofluoro compound of the formula ##STR12## is coupled to the diazo compound of an amine of the formula ##STR13## in the neutral range. Possible buffers are, in particular, the alkali metal salts of fluorides or phosphates.

The reactive dyestuffs of the formula (1) can be isolated and processed to usable, dry dye preparations. The isolation is preferably carried out at the lowest possible temperatures by salting out and filtration. If appropriate, the filtered dyestuffs can be dried by addition of a buffer mixture, for example mono- or disodium phosphate; drying is preferably carried out at temperatures which are not too high and under reduced pressure. In certain cases, the dry preparations according to the invention can be prepared directly, that is to say without intermediate isolation of the dyestuffs, by spray drying the entire mixture prepared.

The new dyestuffs are suitable for dyeing and printing materials containing hydroxyl and amide groups, in particular cellulose materials. They are distinguished by a high reactivity and a high degree of fixing. The dyeings or prints obtainable on cellulose materials with these dyestuffs moreover are distinguished by a high stability of the fibre/dyestuff bond and by an outstanding stability towards oxidising agents, such as detergents containing peroxide or chlorine. The ease of washing out the hydrolysis products formed to only a minor degree during dyeing or printing is excellent. The dyestuffs have good wet fastness properties.

The formulae shown are those of the free acids. The salts, in particular the alkali metal salts, such as sodium, potassium or lithium salts, are in general obtained in the preparation.

The weights mentioned in the examples relate to the free acids. The colour code numbers given in the examples relate to the Colour Index Hue Indication Chart (Indicator Numbers).

EXAMPLE 1

31.9 g of 2-amino-5-hydroxy-naphthalene-1,7-disulphonic acid are dissolved in 400 ml of water to give a neutral solution. 300 g of ice are then added, and 8.8 ml of trifluorotriazine are allowed to run in, a pH of 4.0-4.5 being maintained with 15% strength sodium carbonate solution. The mixture is subsequently stirred for 5 minutes, 8.7 g of morpholine are then added, and a pH of 7.5-8 is maintained with 15% sodium carbonate solution. After 10 minutes at 10° C., the reaction has ended. The reaction product of the formula ##STR14## has partly precipitated.

A diazo compound obtained by the customary route by direct diazotisation of 20.3 g of 1-amino-4-methoxy-benzene-2-sulphonic acid is added to this suspension at 5°-10° C., the pH simultaneously being kept at pH 7.0-7.5 by sprinkling in sodium bicarbonate. When the coupling has ended, the dyestuff of the formula ##STR15## is salted out, filtered off with suction, dried and ground. The red dyestuff powder dissolves readily in water and dyes cotton a clear scarlet (colour code number by a process customary for reactive dyestuffs.

Further valuable dyestuffs which dye cotton a clear scarlet are obtained as described in Example 1 if, instead of morpholine, an equivalent amount of the amines listed below is used.

    ______________________________________                                         Example   Amine                                                                ______________________________________                                          2        Methylamine                                                           3        Ethylamine                                                            4        Dimethylamine                                                         5        Diethylamine                                                          6        Isopropylamine                                                        7        Aminoacetic acid                                                      8        Taurine                                                               9        N-Methyltaurine                                                      10        Methylaminoacetic acid                                               11        β-Sulphatoethylamine                                            12        β-Sulphatoethyl-β-aminoethyl-sulphone                      13        β-Sulphatoethyl-γ-aminopropyl-sulphone                    14        β-Methoxyethylamine                                             15        β-Aminopropionic acid                                           16        Methylaminomethanesulphonic acid                                     17        Ethylaminomethanesulphonic acid                                      18        H.sub.2 NCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                CH.sub.2 OSO.sub.3 3H                                                19        H.sub.2 NCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2 CHCH.sub.               2                                                                    20        H.sub.2 NCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                CH.sub.2 Cl                                                          21        N-Methylbenzylamine                                                  22        1-(β-Aminoethyl)-4-(β-sulphatoethyl-                                 sulphonyl)-benzene                                                   23                                                                                        ##STR16##                                                           24        Cyclohexylamine                                                      25        Ethanolamine                                                         26        N-Methylethanolamine                                                 27        Diethanolamine                                                       28        3-Methoxypropylamine                                                 ______________________________________                                    

EXAMPLE 29

31.9 g of 2-amino-5-hydroxy-naphthalene-1,7-disulphonic acid are dissolved in 400 ml of water to give a neutral solution. 300 g of ice are then added, and 8.8 ml of trifluorotriazine are allowed to run in, a pH of 4.0-4.5 being maintained with 15% strength sodium carbonate solution. The mixture is subsequently stirred for 5 minutes, a neutral solution of 17.3 g of m-sulphanilic acid is then added, and a pH of 5.0-5.5 is maintained with 15% strength sodium carbonate solution. During the acylation, the temperature is allowed to rise to 15°-20°. A diazo compound obtained by the customary route by diazotisation of 20.3 g of 1-amino-4-methoxy-benzene-2-sulphonic acid is added to the resulting solution of the reaction product of the formula ##STR17## at 5°-10°, the pH simultaneously being kept at pH 7.0-7.5 by sprinkling in sodium bicarbonate. When the coupling has ended, the dyestuff of the formula ##STR18## is salted out, filtered off with suction, dried and ground. The red dyestuff powder dissolves readily in water and dyes cotton a clear scarlet (colour code number 6) by a process customary for reactive dyestuffs.

Further valuable dyestuffs which dye cotton a clear scarlet are obtained as described in Example 29 if, instead of m-sulphanilic acid, an equivalent amount of the amines listed below is used.

    ______________________________________                                         Example     Amine                                                              ______________________________________                                         30          Aniline                                                            31          N-Ethylaniline                                                     32          N-Methylaniline                                                    33          4-Chloroaniline                                                    34          3-Chloroaniline                                                    35          2-Chloroaniline                                                    36          o-Toluidine                                                        37          p-Toluidine                                                        38          p-Sulphanilic acid                                                 39          o-Anisidine                                                        40          p-Anisidine                                                        41          4-β-Sulphatoethylsulphonylaniline                             42          3-β-Sulphatoethylsulphonylaniline                             43          β-Sulphatoethyl-4-aminobenzylsulphone                         44          3-Aminobenzoic acid                                                45          4-Aminobenzoic acid                                                46          1-Amino-4-methyl-3-β-sulphatoethyl-                                       sulphonyl-benzene                                                  47          1-Amino-4-vinylsulphonyl-benzene                                   48          1-Amino-3-vinylsulphonyl-benzene                                   ______________________________________                                    

EXAMPLE 49

31.9 g of 2-amino-5-hydroxy-naphthalene-1,7-disulphonic acid are subjected to a condensation reaction with trifluorotriazine and then with morpholine as described in Example 1. A diazo compound obtained by the customary route by direct diazotisation of 28.3 g of 1-amino-4-methoxy-benzene-2,5-disulphonic acid is added to the resulting suspension of the monofluorotriazinyl compound at 5°-10°, the pH simultaneously being kept at 7.0-7.5 by sprinkling in sodium bicarbonate. When the coupling has ended, the dyestuff of the formula ##STR19## is salted out, filtered off with suction, dried and ground. The red dyestuff powder dissolves readily in water and dyes cotton a brilliant reddish-tinged orange (colour code number 5).

If the procedure is as described in this example, but, instead of morpholine, an equivalent amount of the amines mentioned in Examples 2-28 or 29-48 is used, a pH of 5.0-5.5 being maintained during the condensation with the difluorotriazine compound for the aromatic amines mentioned last, reactive dyestuffs which dye cotton scarlet (colour code number 6) similarly result.

EXAMPLE 50

31.9 g of 2-amino-5-hydroxy-naphthalene-1,7-disulphonic acid are subjected to a condensation reaction with trifluorotriazine as described in Example 1. 5.0 g of ethylenediamine are added to the solution of the resulting difluorotriazine compound at 0°, a pH of 5.5-6.5 being maintained. The condensation has ended after 2 to 3 hours. A diazo compound obtained by the customary route by diazotisation of 30.3 g of 2-amino-naphthalene-1,5-disulphonic acid is added to the reaction product of the formula ##STR20## which is largely present as a suspension, the pH simultaneously being kept at pH 7.0-7.5 by sprinkling in sodium bicarbonate. When the coupling has ended, the dyestuff of the formula ##STR21## which has precipitated as a sparingly soluble product, is filtered off with suction and stirred in 1 l of water again. 16.9 g of 2,4,6-trifluoro-5-chloro-pyrimidine are added dropwise at 0°-5°, during which a pH of 7.5-8.0 is maintained with dilute sodium hydroxide solution. The dyestuff dissolves during the condensation reaction. When the condensation has ended (thin layer chromatogram), the dyestuff is salted out, filtered off with suction, dried and ground. The red powder dissolves readily in water and dyes cotton a clear scarlet (colour code number 6).

Further valuable reactive dyestuffs which dye cotton scarlet are obtained as described in this example if, instead of 2,4,6-trifluoro-5-chloropyrimidine, an equivalent amount of the reactive components listed below is used and the condensation reaction is carried out in the temperature range stated.

    ______________________________________                                         Example                                                                               Reactive component   Temperature °C.                             ______________________________________                                         51     4,6-Difluoro-5-chloropyrimidine                                                                     1--15°                                      52     2,4-Dichloro-6-aminotriazine                                                                        25-30°                                      53     2,4-Dichloro-6-(2-sulphophenyl-                                                                     25-30°                                             amino)-triazine                                                         54     2,4-Dichloro-6-(2-sulphophenyl-                                                                     0-5°                                               amino)-triazine                                                         55     2,4-Difluoro-6-(2-chloro-5-                                                                         0-5°                                               sulphophenylamino)-triazine                                             56     2,4-Difluoro-6-aminotriazine                                                                        0-5°                                        ______________________________________                                     

We claim:
 1. Reactive dyestuff which, in the form of the free acid, corresponds to the following formula ##STR22## wherein R=CH₃ or C₂ H₅,R¹ and R², optionally including a further hetero atom, form a heterocyclic ring: R³ =H or SO₃ H.
 2. Reactive dyestuff according to claim 1, wherein R=CH₃.
 3. Reactive dyestuff according to claim 1, wherein R¹ and R², optionally including a further hetero atom, form a heterocyclic 5- or 6-membered ring.
 4. Reactive dyestuff according to claim 1, wherein ##STR23## denotes the radical of the formula ##STR24##
 5. Reactive dyestuff according to claim 1, of the formula ##STR25##
 6. Process for dyeing or printing materials containing hydroxyl or amide groups with a reactive dyestuff, by applying thereto a reactive dyestuff according to claim 1 is used. 